One-pot conversion of cellulose to isosorbide using supported metal catalysts and ion-exchange resin

Article abstract of DOI:10.1016/j.catcom.2015.04.009

One-pot conversion of cellulose to isosorbide was investigated by supported metal catalysts and ion-exchange resin in water. The maximum isosorbide yield using supported platinum catalysts and Amberlyst 70 was less than 30%. The isosorbide yield drastically increased with supported ruthenium catalysts instead of supported platinum catalysts and it also increased with the loading of ruthenium on carbon support. One-pot conversion of cellulose to isosorbide by 4 wt.% ruthenium catalyst and Amberlyst 70 proceeded with isosorbide yield of 55.8%.

Full text of DOI:10.1016/j.catcom.2015.04.009

Catalysis Communications 67 (2015) 59–63
Contents lists available at ScienceDirect
Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom
Short communication
One-pot conversion of cellulose to isosorbide using supported metal
catalysts and ion-exchange resin
a
a
c
Aritomo Yamaguchi a,b, , Osamu Sato , Naoki Mimura , Masayuki Shirai
⁎
a
Research Center for Compact Chemical System, National Institute of Advanced Industrial Science and Technology (AIST), 4-2-1 Nigatake, Miyagino, Sendai 983-8551, Japan
JST, PRESTO, 4-2-1 Nigatake, Miyagino, Sendai 983-8551, Japan
Department of Chemistry and Bioengineering, Faculty of Engineering, Iwate University, Ueda 4-3-5, Morioka 020-8551, Japan
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
One-pot conversion of cellulose to isosorbide was investigated by supported metal catalysts and ion-exchange
resin in water. The maximum isosorbide yield using supported platinum catalysts and Amberlyst 70 was less
than 30%. The isosorbide yield drastically increased with supported ruthenium catalysts instead of supported
platinum catalysts and it also increased with the loading of ruthenium on carbon support. One-pot conversion
of cellulose to isosorbide by 4 wt.% ruthenium catalyst and Amberlyst 70 proceeded with isosorbide yield of
55.8%.
Received 25 February 2015
Received in revised form 1 April 2015
Accepted 2 April 2015
Available online 3 April 2015
Keywords:
Biomass conversion
Cellulose
© 2015 Elsevier B.V. All rights reserved.
Isosorbide
Sugar alcohol
Heterogeneous catalysis
1. Introduction
[25,26]. In these processes, however, neutralization procedure is essen-
tial to remove homogeneous acid catalysts and also separation process-
Conversion of lignocellulosic biomass to fuels and chemicals has
greatly attracted attention for establishing the sustainable society be-
cause of the abundance and renewability of the lignocellulose [1–3].
Cellulose, a polymer of D-glucose, is the most abundant component of
biomass; thus, valorization of cellulose is an issue of great interest.
Recently, cellulose conversion to sorbitol has been reported by some
research groups (Scheme 1) [4–12]. Subsequently, dehydration of sorbi-
tol can provide valuable chemicals: both anhydrosorbitol (sorbitan) and
isosorbide (Scheme 1) [13–19]. Anhydrosorbitol is a key material for
producing sorbitan fatty acid esters, which are used as naturally-
derived surfactants or nontoxic food additives. Isosorbide is a drug med-
icine used as osmotic diuretics and blood-pressure-lowering drugs.
Also, isosorbide has attracted a great deal of attention because poly
(ethylene terephthalate) (PET) containing isosorbide has higher glass
transition temperatures than pure PET [13,20–22], broadening the
applications of polyesters. Consequently, the cellulose valorization can
be realized by conversion of cellulose to isosorbide or anhydrosorbitol.
One-pot conversion of cellulose to isosorbide has been reported using
a combination of supported metal catalyst and homogeneous acid
such as sulfuric acid [23], hydrochloric acid [24], and heteropoly acid
es of products from the salt solutions are required. Thus, the usage of
heterogeneous acid catalyst is desirable for easy separation of the prod-
ucts. Li et al. reported that ruthenium supported on niobium phosphate
showed high activity for cellulose conversion to isosorbide (maximum
yield 52%) [27]. Further improvement of catalyst system such as combi-
nation of supported metal catalyst and solid acid is required for the
higher isosorbide yield. In this work, we found that the combination
of supported ruthenium catalysts and ion-exchange resin, Amberlyst
70, was effective for one-pot conversion of cellulose to isosorbide
(Scheme 1). Recently, Shrotri et al. reported transfer hydrogenation of
cellulose-based oligomers to sorbitol in a fixed-bed reactor [28], leading
to the technique for the direct conversion of cellulose into isosorbide
using a flow reactor.
2. Experimental
2.1. Catalyst preparation
The supported platinum catalysts were prepared by an impregna-
tion method using a carbon black BP2000 (Cabot Corporation) and a
nitric acid aqueous solution of cis-[Pt(NH3)2(NO2)2] (Furuya Metal Co.,
Ltd.) as follows. The aqueous solution of platinum precursor and the
carbon black were stirred for 12 h at ambient temperature and evapo-
rated to dryness at 323 K under reduced pressure by a rotary evaporator.
Then the samples were dried for 10 h at 373 K in an oven, followed by
⁎
Corresponding author at: Research Center for Compact Chemical System, National
Institute of Advanced Industrial Science and Technology (AIST), 4-2-1 Nigatake,
Miyagino, Sendai 983-8551, Japan.
E-mail address: a.yamaguchi@aist.go.jp (A. Yamaguchi).
http://dx.doi.org/10.1016/j.catcom.2015.04.009
1566-7367/© 2015 Elsevier B.V. All rights reserved.

60
A. Yamaguchi et al. / Catalysis Communications 67 (2015) 59–63
Scheme 1. One-pot conversion of cellulose to isosorbide.
treatment at 673 K for 2 h under flowing hydrogen. The amounts of plat-
inum in the catalysts were 2 and 4 wt.%, of which the catalysts were rep-
resented as 2%Pt/C and 4%Pt/C, respectively.
The supported ruthenium catalysts were also prepared by an im-
pregnation method using BP2000 and an aqueous solution of RuCl3
(Wako Pure Chemical Industries, Ltd.). The preparation process of sup-
ported ruthenium catalysts (2%Ru/C and 4%Ru/C) was same as that of
platinum catalysts.
3. Results and discussion
Sorbitol was obtained from cellulose by hydrogenolysis, combina-
tion of hydrolysis and hydrogenation, using supported platinum cata-
lyst (2%Pt/C) and hydrogen (5 MPa) in water at 463 K for 16 h with a
yield of sorbitol 60.2% (Table S1 and characterization result of the Pt/C
catalyst are shown in ESI) [4,29,30]. Also, isosorbide could be obtained
from sorbitol by dehydration using ion-exchange resin Amberlyst 70
1 g at 463 K for 16 h with a yield of isosorbide 62.9% (Table S2),
where the maximum operating temperature of Amberlyst 70 was
463 K, as shown in its instructions. Accordingly, we carried out one-
pot conversion of cellulose to isosorbide using the Pt/C catalyst and
Amberlyst 70 at 463 K for 16 h, resulting in 8.4% of isosorbide yield
(Table 1). The isosorbide yield obtained by the one-pot reaction (8.4%)
was much lower than the expected yield (38%) from stepwise reactions
(first step 60.2% and second step 62.9%). The conversion of cellulose to
isosorbide consists of cellulose hydrolysis, glucose hydrogenation, and
sorbitol dehydration (Scheme 1). The acid catalyst Amberlyst 70 can
enhance not only sorbitol dehydration but also cellulose hydrolysis;
thus, it enables lower reaction temperature than 463 K. The isosorbide
yield increased to 9.3% at 453 K (Table 1); however, it decreased to
6.5% at 443 K where the yield of sorbitol increased with decreasing reac-
tion temperature, indicating that sorbitol dehydration was slow at
lower temperature. Next, we changed the amount of the acid catalyst
to accelerate the sorbitol dehydration. The isosorbide yield increased
with increasing the amount of Amberlyst 70 and it reached 16.1% in
the case of 3 g of Amberlyst 70 at 453 K (Table 2). Pt loadings and cata-
lyst amounts were also investigated for the enhancement of the
isosorbide yield from the cellulose (Table 3). The sizes of metal particle
in 2%Pt/C and 4%Pt/C were 1.7 nm and 1.9 nm from hydrogen adsorp-
tion, respectively [30]. The isosorbide yield was increased from 16.1%
The ion-exchange resin, Amberlyst 70, was purchased from The Dow
Chemical Company and used without further purification.
2.2. Reaction procedure
Cellulose (Merck KGaA) was pulverized with a ball mill at 60 rpm for
48 h. The conversion of cellulose was carried out in a batch reactor (OM
Lab-Tech, MMJ-100), of which inner volume was 100 cm3 [4,29]. The
cellulose (0.324 g), the supported metal catalyst (0.1–0.4 g), Amberlyst
70 (0.5–3 g), and water (40 g) were loaded in the reactor and
the reactor was purged with hydrogen gas, and then hydrogen gas
(5 MPa) was loaded in the reactor at ambient temperature. The reactor
was heated to 443–463 K and maintained at the reaction temperature
for the reaction time (16 h) with screw stirring at 600 rpm. After the
reaction, a mixture of liquid and solid was recovered and filtered to sep-
arate the solid materials from the liquid fraction. The quantitative anal-
ysis of water-soluble products in the liquid fraction was conducted by
high-performance liquid chromatography (Shimadzu, HPLC) with a
refractive index detector (Shimadzu, RID-10A) and a UV–Vis detector
(Shimadzu, SPD-20AV) equipped with a Rezex RPM-Monosaccharide
Pb + 2 (8%) (Phenomenex) and a SUGAR SC1211 column (Shodex).
Amount of total organic carbon (TOC) in the liquid fraction was deter-
mined using a total organic carbon analyzer (Shimadzu, TOC-VCSN).
The other water-soluble (WS) products defined in this manuscript
were calculated from the amount of total organic carbon in the liquid
fraction other than the amount of total carbon detected by HPLC. The
product yield was calculated based on glucose unit in the reactant
cellulose.
Some of the recovered solid fractions by filtration after the reaction
were loaded in the reactor again to investigate the reusability of the cat-
alysts, and then 0.324 g of fresh cellulose was also loaded in the reactor.
The reaction was carried out in the same method as identified above.
Sorbitol dehydration reaction was also carried out in a batch
reactor (OM Lab-Tech, MMJ-100). The sorbitol aqueous solution
(0.05 mol dm−3, 40 cm3) and Amberlyst 70 1 g were loaded in the
reactor and the reactor was purged with helium gas, and then the reac-
tor was heated to 463 K and maintained at the temperature for 16 h
with screw stirring at 600 rpm.
Table 1
Product yields obtained from conversion of milled cellulose using 2%Pt/C and Amberlyst
70 with 5 MPa H2 for 16 h (milled cellulose 0.324 g, 2%Pt/C 0.2 g, Amberlyst 70 1.0 g).
Ta (K)
Yield (%)
ISb
1,4-AHSOc
SOd
IMe
MAf
Other WSg
443
453
463
6.5
9.3
8.4
2.9
0.3
0.2
24.2
12.4
0.8
0.5
0.5
0.4
3.2
1.1
0.0
20.2
21.5
18.2
a
Reaction temperature.
Isosorbide.
1,4-Anhydrosorbitol.
Sorbitol.
Isomannide.
Mannitol.
b
c
d
e
f
g
Other water-soluble products.

A. Yamaguchi et al. / Catalysis Communications 67 (2015) 59–63
61
Table 2
Table 4
Product yields obtained from conversion of milled cellulose using 2%Pt/C and Amberlyst
70 at 453 K with 5 MPa H2 for 16 h (milled cellulose 0.324 g, 2%Pt/C 0.2 g).
Product yields obtained from conversion of milled cellulose using 4%Ru/C and Amberlyst
70 with 5 MPa H2 for 16 h (milled cellulose 0.324 g, 4%Ru/C 0.2 g, Amberlyst 70 3.0 g).
Resina (g)
Yield (%)
ISb
Ta (K)
Yield (%)
ISb
1,4-AHSOc
SOd
IMe
MAf
Other WSg
1,4-AHSOc
SOd
IMe
MAf
Other WSg
0.5
7.0
9.3
16.1
2.7
0.3
9.2
20.1
12.4
2.2
0.2
0.5
0.7
3.4
1.1
0.2
19.7
21.5
8.9
443
453
463
31.8
39.6
55.8
42.5
35.4
16.1
3.2
0.8
0.0
1.8
2.0
3.3
0.1
0.0
0.0
5.0
1.2
2.3
1.0h
3.0
a
a
Amount of Amberlyst 70.
Isosorbide.
1,4-Anhydrosorbitol.
Sorbitol.
Isomannide.
Mannitol.
Reaction temperature.
Isosorbide.
1,4-Anhydrosorbitol.
Sorbitol.
Isomannide.
Mannitol.
b
c
b
c
d
e
f
d
e
f
g
h
g
Other water-soluble products.
Same data in Table 1.
Other water-soluble products.
inhibited by Amberlyst 70; on the other hand, the Ru/C catalyst worked
well for cellulose hydrogenolysis even with Amberlyst 70. Zhao et al.
also reported the similar results that Ru/C was more active for cellulose
conversion to isosorbide with hydrochloric acid or sulfuric acid [24]. The
reported maximum isosorbide yield from one-pot conversion of cellu-
lose was 52% using Ru/C and heteropoly acid [26] and Ru/niobium phos-
phate [27]. The one-pot conversion of cellulose to isosorbide consists of
cellulose hydrolysis, glucose hydrogenation, and sorbitol dehydration.
5-Hydroxymethylfurfural (HMF) is also reported as one of the promis-
ing chemicals from cellulosic biomass, which is reviewed in some arti-
cles [32,33]. HMF can be obtained by cellulose hydrolysis, glucose
isomerization, and fructose dehydration. These reactions also proceed
using acid catalysts; however, the HMF yield is not so high (ca. 30%)
unless ionic liquid or organic solvent was used [32,33]. In this study,
we obtained isosorbide (yield 55.8%) and a trace amount of HMF can
be obtained, indicating that glucose hydrogenation into sorbitol was
faster than glucose isomerization to fructose under the reaction condi-
tion with acid catalyst, supported metal catalyst, and high-pressure
hydrogen. We also investigated the effects of Ru loadings and catalyst
amounts on the isosorbide yield from the cellulose (Table 5). The
isosorbide yields using 4%Ru/C 0.1 g (29.4%) or 0.3 g (42.1%) were
lower than that using 4%Ru/C 0.2 g (55.8%), indicating that optimum
amount of 4%Ru/C was 0.2 g. In the case of 0.1 g of 4%Ru/C, the yield
of the other water-soluble products was higher than those using 0.2
or 0.3 g, implying that the hydrogenation of glucose was slow because
of less number of ruthenium metal sites. Interestingly, the isosorbide
yield using 2%Ru/C 0.4 g (24.1%) was much lower than that using
4%Ru/C 0.2 g (55.8%) despite the same amount of Ru atoms on these cat-
alysts. The metal dispersion of 2%Ru/C catalyst was 50.7% (Ru metal size
2.6 nm), which was twice larger than that of 4%Ru/C (25.0%, Ru metal
size 5.3 nm); thus, the number of surface Ru atoms in 4%Ru/C 0.2 g
(isosorbide yield 55.8%) was almost the same as that in 2%Ru/C 0.2 g
to 24.7% by an increase of 2%Pt/C catalyst amount from 0.2 to 0.3 g. On
the other hand, the isosorbide yield over 0.1 g of 4%Pt/C (16.8%) was
almost the same as that over 0.2 g of 2%Pt/C (16.1%) when the amounts
of Pt surface atoms were almost the same. The isosorbide yield over
4%Pt/C increased with increasing catalyst amount and reached 29.9%
using 0.3 g of 4%Pt/C; however, the obtained yield of isosorbide was
still lower than the expected yield in the case of Pt/C catalysts.
The supported ruthenium catalysts were also reported to be active
for the cellulose hydrogenolysis to sorbitol [5–7,11,29,31]. The sorbitol
yield from cellulose was 51.2% at 463 K for 16 h, using supported ruthe-
nium catalyst (4%Ru/C) and hydrogen (5 MPa) (Table S3 and character-
ization result of the Ru/C catalyst are shown in ESI). The Ru/C catalyst
was comparably active to the Pt/C catalyst for the cellulose hydroly-
sis to sorbitol (Tables S1 and S3) in agreement with the previous
reports [29,31]. We carried out one-pot conversion of cellulose to
isosorbide using 4%Ru/C catalyst and Amberlyst 70 for 16 h (Table 4).
The isosorbide yields using Ru/C were much higher than those using
Pt/C catalysts. The total yield of sorbitol-derived materials, which
were sorbitol, 1,4-anhydrosorbitol, and isosorbide, decreased with in-
creasing reaction temperature. On the other hand, the isosorbide yield
was higher at higher reaction temperature, indicating that the dehydra-
tion of sorbitol to isosorbide proceeded at high reaction temperature
and at the same time side reaction also proceeded slightly. The
isosorbide yield (55.8%) over 4%Ru/C and Amberlyst 70 was higher
than the expected yield (32%) from stepwise reactions (first step
51.2% and second step 62.9%). We found that the Ru/C catalyst was
more active than the Pt/C catalyst for the direct cellulose conversion
to isosorbide with Amberlyst 70. The activity for cellulose into sorbitol
using Ru/C was almost the same as that using Pt/C; however, the activ-
ity for cellulose into isosorbide using Ru/C and Amberlyst 70 was higher
than that using Pt/C and Amberlyst 70. The activity of platinum was
Table 3
Table 5
Product yields obtained from conversion of milled cellulose using Pt/C and Amberlyst 70 at
453 K with 5 MPa H2 for 16 h (milled cellulose 0.324 g, Amberlyst 70 3.0 g).
Product yields obtained from conversion of milled cellulose using Ru/C and Amberlyst
70 at 463 K with 5 MPa H2 for 16 h (milled cellulose 0.324 g, Amberlyst 70 3.0 g).
Cata
Yield (%)
ISb
Cata
Yield (%)
ISb
1,4-AHSOc
SOd
IMe
MAf
Other WSg
1,4-AHSOc
SOd
IMe
MAf
Other WSg
2%Pt/C, 0.2 gh
2%Pt/C, 0.3 g
4%Pt/C, 0.1 g
4%Pt/C, 0.2 g
4%Pt/C, 0.3 g
16.1
24.7
16.8
27.3
29.9
9.2
13.2
9.9
16.9
16.8
2.2
0.5
7.7
2.8
0.7
0.7
0.8
0.8
1.0
1.1
0.2
0.1
0.3
0.3
0.1
8.9
5.5
16.7
8.6
5.4
2%Ru/C, 0.2 g
2%Ru/C, 0.4 g
4%Ru/C, 0.1 g
4%Ru/C, 0.2 gh
4%Ru/C, 0.3 g
13.2
24.1
29.4
55.8
42.1
3.5
0.1
0.6
0.6
0.0
0.6
0.5
0.5
0.4
3.3
2.4
0.4
0.0
0.6
0.0
0.0
14.2
6.4
15.6
2.3
15.7
18.6
16.1
24.4
3.1
a
a
Catalysts.
Isosorbide.
1,4-Anhydrosorbitol.
Sorbitol.
Isomannide.
Mannitol.
Catalysts.
Isosorbide.
1,4-Anhydrosorbitol.
Sorbitol.
Isomannide.
Mannitol.
b
b
c
c
d
e
f
d
e
f
g
h
g
h
Other water-soluble products.
Same data in Table 2.
Other water-soluble products.
Same data in Table 4.

62
A. Yamaguchi et al. / Catalysis Communications 67 (2015) 59–63
Fig. 1. Recycling results for the one-pot conversion of cellulose to isosorbide using 4%Ru/C and Amberlyst 70 at (a) 463, (b) 453, and (c) 443 K with 5 MPa H2 for 16 h (milled cellulose
0.324 g, 4%Ru/C 0.2 g, Amberlyst 70 3.0 g). IS: isosorbide, 1,4-AHSO: 1,4-anhydrosorbitol, SO: sorbitol.
(isosorbide yield 13.2%). These results indicated that the active rutheni-
um species were formed in 4%Ru/C. Li et al. investigated the size effect
of ruthenium metal particles on cellulose conversion to isosorbide
[27] and showed that Ru metal particles with 5.5 nm showed the
highest isosorbide yield. In this study, we also showed that 4%Ru/C
with 5.3 nm of Ru metal particles provided the higher isosorbide yield
than 2%Ru/C with 2.6 nm of Ru metal particles. We have succeeded in
one-pot conversion of cellulose to isosorbide (yield 55.8%) by supported
ruthenium catalysts and ion-exchange resin, Amberlyst 70, in water
without homogeneous acid catalysts.
Hirokazu Kobayashi of Hokkaido University for helpful technical discus-
sions about the experimental setup.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.catcom.2015.04.009.
References
The reusability of the catalysts, 4%Ru/C and Amberlyst 70, was inves-
tigated by using them three times. These catalysts were recovered by
filtration after the reaction and used without any treatment three
times. The fresh cellulose was added each time and the yields were cal-
culated based on the amount of fresh cellulose. The isosorbide yield at
463 K decreased from 55.8% (1st run) to 10.6% (2nd run) where the
1,4-AHSO also decreased from 16.1% to 4.2% (Fig. 1), indicating that
the Ru/C catalyst deactivated and glucose hydrogenation did not
proceed effectively. We confirmed that ruthenium species were not
detected in water-soluble fraction after the reaction by ICP measure-
ment, indicating that ruthenium species remained on the carbon
support. The reason of the catalyst deactivation might be carbon precip-
itation on the ruthenium surface after the 1st run of the reaction. The
reusability of the catalysts at lower reaction temperature became better.
At 443 K, the yields of isosorbide and 1,4-anhydrosorbitol decreased
from 31.8% and 42.5% (1st run) to 20.3% and 29.9% (2nd run), respec-
tively. At low temperature, the side reactions such as polymerization
might be slow and carbon precipitation might be less adsorbed on the
metal surface; thus, the activity of ruthenium catalyst could be kept rel-
atively. The isosorbide yield at the 3rd run became only 4.8% even at
443 K. The catalyst life time and regeneration method should be devel-
oped, which we must consider next.
[1] A. Corma, S. Iborra, A. Velty, Chemical routes for the transformation of biomass into
chemicals, Chem. Rev. 107 (2007) 2411–2502.
[2] G.W. Huber, J.N. Chheda, C.J. Barrett, J.A. Dumesic, Production of liquid alkanes by
aqueous-phase processing of biomass-derived carbohydrates, Science 308 (2004)
1446–1450.
[3] J.N. Chheda, G.W. Huber, J.A. Dumesic, Liquid-phase catalytic processing of biomass-
derived oxygenated hydrocarbons to fuels and chemicals, Angew. Chem. Int. Ed. 46
(2007) 7164–7183.
[4] A. Fukuoka, P.L. Dhepe, Catalytic conversion of cellulose into sugar alcohols, Angew.
Chem. Int. Ed. 45 (2006) 5161–5163.
[5] C. Luo, S. Wang, H. Liu, Cellulose conversion into polyols catalyzed by reversibly
formed acids and supported ruthenium clusters in hot water, Angew. Chem. Int.
Ed. 46 (2007) 7636–7639.
[6] J. Geboers, S.V. de Vyver, K. Carpentier, K. de Blochouse, P. Jacobs, B. Sels, Efficient
catalytic conversion of concentrated cellulose feeds to hexitols with heteropoly
acids and Ru on carbon, Chem. Commun. 46 (2010) 3577–3579.
[7] M. Liu, W. Deng, Q. Zhang, Y. Wang, Y. Wang, Polyoxometalate-supported rutheni-
um nanoparticles as bifunctional heterogeneous catalysts for the conversions of
cellobiose and cellulose into sorbitol under mild conditions, Chem. Commun. 47
(2011) 9717–9719.
[8] S. Van de Vyver, J. Geboers, M. Dusselier, H. Schepers, T. Vosch, L. Zhang, G. Van
Tendeloo, P.A. Jacobs, B.F. Sels, Selective bifunctional catalytic conversion of cellu-
lose over reshaped Ni particles at the tip of carbon nanofibers, ChemSusChem 3
(2010) 698–701.
[9] P. Yang, H. Kobayashi, K. Hara, A. Fukuoka, Phase change of nickel phosphide cata-
lysts in the conversion of cellulose into sorbitol, ChemSusChem 5 (2012) 920–926.
[10] L.-N. Ding, A.-Q. Wang, M.-Y. Zheng, T. Zhang, Selective transformation of cellulose
into sorbitol by using a bifunctional nickel phosphide catalyst, ChemSusChem 3
(2010) 818–821.
4. Conclusions
[11] W. Deng, X. Tan, W. Fang, Q. Zhang, Y. Wang, Conversion of cellulose into sorbitol
over carbon nanotube-supported ruthenium catalyst, Catal. Lett. 133 (2009)
167–174.
[12] M. Yabushita, H. Kobayashi, A. Fukuoka, Catalytic transformation of cellulose into
platform chemicals, Appl. Catal. B 145 (2014) 1–9.
[13] R.C. Hockett, H.G. Fletcher Jr., E.L. Sheffield, R.M. Goepp Jr., Hexitol anhydrides.
The structure of isosorbide, a crystalline dianhydrosorbitol, J. Am. Chem. Soc. 68
(1946) 927–930.
[14] K. Bock, C. Pedersen, H. Thogersen, Acid catalyzed dehydration of alditols. Part 1.
D-Glucitol and D-mannitol, Acta Chem. Scand. B 35 (1981) 441–449.
[15] G. Fleche, M. Huchette, Isosorbide; preparation, properties and chemistry, Starch 38
(1986) 26–30.
We have succeeded in converting cellulose into isosorbide directly
with 55.8% yield by a supported ruthenium catalyst and Amberlyst 70
in water. It has been demonstrated that the direct catalytic conversion
of cellulose into useful chemicals is a powerful technique for the use
of lignocellulosic biomass.
Acknowledgment
[16] A. Yamaguchi, N. Hiyoshi, O. Sato, M. Shirai, Sorbitol dehydration in high tempera-
ture liquid water, Green Chem. 13 (2011) 873–881.
This study was supported by a Grant-in-Aid for Young Scientists
(A) Grant Number 25708028 from Japan Society for the Promotion of
Science (JSPS) and the New Chemical Technology Research Encourage-
ment Award Grant Number H22-9 from Japan Association of Chemical
Innovation (JACI). We acknowledge Prof. Atsushi Fukuoka and Prof.
[17] P. Sun, X. Long, H. He, C. Xia, F. Li, Conversion of cellulose into isosorbide over bifunc-
tional ruthenium nanoparticles supported on niobium phosphate, ChemSusChem 6
(2013) 2190–2197.
[18] Y. Morita, S. Furusato, A. Takagaki, S. Hayashi, R. Kikuchi, S.T. Oyama, Intercalation-
controlled cyclodehydration of sorbitol in water over layered-niobium-molybdate
solid acid, ChemSusChem 7 (2014) 748–752.

A. Yamaguchi et al. / Catalysis Communications 67 (2015) 59–63
63
[19] A. Yamaguchi, O. Sato, N. Mimura, M. Shirai, Intramolecular dehydration of mannitol
in high-temperature liquid water without acid catalysts, RSC Adv. 4 (2014)
45575–45578.
[27] P. Sun, X. Long, H. He, C. Xia, F. Li, Conversion of cellulose into isosorbide over bifunc-
tional ruthenium nanoparticles supported on niobium phosphate, ChemSusChem 6
(2013) 2190–2197.
[20] M. Beldi, R. Medimagh, S. Chatti, S. Marque, D. Prim, A. Loupy, F. Delolme, Character-
ization of cyclic and non-cyclic poly-(ether-urethane)s bio-based sugar diols by a
combination of MALDI-TOF and NMR, Eur. Polym. J. 43 (2007) 3415–3433.
[21] F. Fenouillot, A. Rousseau, G. Colomines, R. Saint-Loup, J.-P. Pascault, Polymers
from renewable 1,4:3,6-dianhydrohexitols (isosorbide, isomannide and isoidide):
a review, Prog. Polym. Sci. 35 (2010) 578–622.
[28] A. Shrotri, H. Kobayashi, A. Tanksale, A. Fukuoka, J. Beltramini, Transfer hydrogena-
tion of cellulose-based oligomers over carbon-supported ruthenium catalyst in a
fixed-bed reactor, ChemCatChem 6 (2014) 1349–1356.
[29] H. Kobayashi, Y. Ito, T. Komanoya, Y. Hosaka, P.L. Dhepe, K. Kasai, K. Hara, A.
Fukuoka, Synthesis of sugar alcohols by hydrolytic hydrogenation of cellulose over
supported metal catalysts, Green Chem. 13 (2011) 326–333.
[22] J. Wu, P. Eduard, L. Jasinska-Walc, A. Rozanski, B.A.J. Noordover, D.S. van Es, C.E.
Koning, Fully isohexide-based polyesters: synthesis, characterization, and
structure–properties relations, Macromolecules 46 (2013) 384–394.
[23] R. Palkovits, K. Tajvidi, J. Procelewska, R. Rinaldi, A. Ruppert, Hydrogenolysis of
cellulose combining mineral acids and hydrogenation catalysts, Green Chem. 12
(2010) 972–978.
[30] A. Yamaguchi, O. Sato, N. Mimura, Y. Hirosaki, H. Kobayashi, A. Fukuoka, M. Shirai,
Direct production of sugar alcohols from wood chips using supported platinum
catalysts in water, Catal. Commun. 54 (2014) 22–26.
[31] H. Kobayashi, T. Komanoya, S.K. Guha, K. Hara, A. Fukuoka, Conversion of cellulose
into renewable chemicals by supported metal catalysis, Appl. Catal. A 409–410
(2011) 13–20.
[24] G. Liang, C. Wu, L. He, J. Ming, H. Cheng, L. Zhuo, F. Zhao, Selective conversion of con-
centrated microcrystalline cellulose to isosorbide over Ru/C catalyst, Green Chem.
13 (2011) 839–842.
[25] R. Palkovits, K. Tajvidi, A.M. Ruppert, J. Procelewska, Heteropoly acids as efficient
acid catalysts in the one-step conversion of cellulose to sugar alcohols, Chem.
Commun. 47 (2011) 576–578.
[32] I. Agirrezabal-Telleria, I. Gandarias, P.L. Arias, Heterogeneous acid-catalysts for the
production of furan-derived compounds (furfural and hydroxymethylfurfural)
from renewable carbohydrates: a review, Catal. Today 234 (2014) 42–58.
[33] A. Mukherjee, M.-J. Dumont, V. Raghavan, Review: sustainable production of
hydroxymethylfurfural and levulinic acid: challenges and opportunities, Biomass
Bioenergy 72 (2015) 143–183.
[26] B. Op de Beeck, J. Geboers, S. Van de Vyver, J. Van Lishout, J. Snelders, W.J.J. Huijgen,
C.M. Courtin, P.A. Jacobs, B.F. Sels, Conversion of (ligno)cellulose feeds to isosorbide
with heteropoly acids and Ru on carbon, ChemSusChem 6 (2013) 199–208.