Catalysis Today 195 (2012) 136143

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Catalysis Today
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Production of 1,5-pentanediol from biomass via furfural and

tetrahydrofurfuryl alcohol
Yoshinao Nakagawa, Keiichi Tomishige

Department of Applied Chemistry, School of Engineering, Tohoku University, 6-6-07 Aoba, Aramaki, Aoba-ku, Sendai 980-8579, Japan

article info
Article history:
Received 11 January 2012
Received in revised form 15 March 2012 Accepted 26
April 2012
Available online 2 June 2012
Keywords:
Hydrogenolysis
Biomass
Tetrahydrofurfuryl alcohol
Rhodium
Heterogeneous catalysis

star
ch,
cellu
lose
1. Introduction
and
Biomass
has
beenhem
received much attention asicell
renewable
organiculos
resources.
Convertinge
biomass into high-qualityare
transportation
fuels
andwide
valuable chemicals is calledly
biorefinery, which is expectedavail
to
be
substituted
forable
petrorefinery in the future [1.
6].
While
elec-tricityBec
generated
from
variousaus
renewable resources such ase
wind and solar power can bethes
utilized for transportation,e
organic chem-icals cannot bemat
produced
from
mosterial
renewable resources excepts
biomass.
Therefore,cont
development
of
theain
production
systems
ofhigh
chemicals,
especiallyer
monomers for plastics withamo
large demands, is criticallyunt
important for sustainableof
society.
oxyg
Carbohydrates includingen

abstra
ct
Production
of
1,5pentanediol
from
tetrahydrofu
rfuryl
alcohol,
which can
be produced
from
biomass via
furfural, is

reviewed. Silica- or carbon-supported

rhodium catalysts modified with Re, Mo or W
show high activity and selectivity, while
commercial hydrogenation catalysts such as
Ru/C, copper chromite and Raney Ni show
much lower activity and selectivity. The
formation of metal bond between rhodium
metal particles and additive metal is a key to
the high performance. The reaction
mechanism is discussed based on the
characterization data, reactivity of related
substrates and kinetics.
2012 Elsevier B.V. All rights reserved.

than most plastics,of

furan
reactions that cancompounds into
remove oxygen atomsthe
from substrates aretetrahydrofuran
essential in the sugarbased biorefinery [7].
These
reactions
include
dehydration 1
and C O hydrogenoly- Corres
sis. While direct C O
pond
hydrogenolysis
of
sugars is very difficult,
ing
dehydration of sugar
auth
monomers gives furan
derivatives over acid
or.
catalysts (Fig. 1) [8
Tel.:
12].
In
particular,
+81
dehydration of xylose,
which can be obtained
22
from
hemicellulose,
795
into furfural is a wellknown reaction and is
7215
currently carried out in
; fax:
an industrial scale.
Dehydration
of
+81
hexoses
such
as
22
fructose and glucose
into
5- 795
hydroxymethylfurfural
7215
has been extensively
. Estudied
in
these
years. Hydrogenation
mail

addr
ess:
tomi
@er
ec.ch
e.toh
oku.
ac.jp
(K.
Tomi
shige
).

mec
hani
derivatives such as furfuralsm
into tetrahydrofurfuryl alcoholare
(THFA) can be achieved overalso
nickel-based catalysts [13disc
15].
Therefore,usse
tetrahydrofuran derivatives,d.
THFA in particular, can be
regarded
as
renewable2.
building blocks. This reviewRea
concerns
the
recentctio
n
developments
of
the
net
selective hydrogenolysis ofwor
THFA into valu-able alcoholsk of
by our and some otherTHF
research groups. Very highA
selectivity to 1,5-pentanediolhyd
(1,5-PeD) can be obtainedrog
over Rh-based catalystsenol
ysis
modified
with
transition
metals. The structure of the
T
active sites and the reaction
he
0920-5861/$ see front matter
2012 Elsevier B.V. All rights
reserved.
http://dx.doi.org/10.1016/j.catto
d.2012.04.048

reactions involved inreactions in the

THFA hydrogenolysisgas phase with
are displayed in Fig.G2MP2
level
2. There are three Ctheory (Table 1).
O bonds in THFAAll
the
molecule, and the pri-hydrogenolysis
mary products of C Oreactions have
hydrogenolysis
arelarge negative G
1,5-PeD,
1,2-values, showing
pentanediol (1,2-PeD)that
the
and
2-reactions
are
methyltetrahydrofuran essentially
. Overhydrogenolysisirreversible. The
gives 1-pentanol (1-forma-tion of 1,2PeOH) from both 1,2-PeD is more
and 1,5-PeDs and 2-exothermic than
pentanol
(2-PeOH)that of 1,5-PeD.
from 1,2-PeD. C CTherefore, if the
hydrogenolysis
formations
of
(d5/30/2012 degrada-1,2- and 1,5tion) gives C4 or lowerPeDs proceed in
compounds.
Wethe same mechcalculated
theanism over an
energetics of theseessentially

nonselective
catalyst,
the
selectivity to 1,2PeD may well be
higher than that
to 1,5-PeD. The
selective
formation of 1,5PeD requires the
use
of
very
selective
catalysts.
The
formation
reaction of 2methyltetrahydro
furan
has
a
larger change in
free
energies
than those of
PeDs because
the formation of
PeDs

Y. Nakagawa, K. Tomishige / Catalysis Today 195 (2012) 136143

137

Fig. 1. Furan and tetrahydrofuran derivatives produced from biomass.

Table 1
Calculated energetics of THFA hydrogenolysis at
G2MP2 level theory (298.15 K, 1 atm in gas phase).

3. Rh-based catalysts
3.1. Performances of

Reaction

supported Rh MOx catalysts

(i) THFA + H2 1,5-PeD

(ii) THFA + H2 1,2-PeD

Rhodium is a catalytically
active element for C O
hydrogenol-ysis under the
conditions of high pressure

(iii) THFA + H2 2-methyltetrahydrofuran + H2 O

H2
(10
MPa)
and
temperature around 373 K.
Our group has tested various
monometallic
supported
noble-metal catalysts in the
hydrogenol-ysis of aqueous
glycerol
[22].
Rh/SiO2
showed the highest activity
and selectivity to C O
dissociation in the catalysts
tested (Rh, Ru, Pd and Pt
Fig. 2. Reaction routes in THFA
hydrogenolysis.

supported on SiO2 , C and

as methylfuran and dimethylfuran [27,28]. Modification of

Rh/SiO2 with Re, Mo or W is
very effective to enhance the
catalytic performance [24].
The modi-fied catalysts are
prepared
by
sequential
impregnation method
using RhCl3 , NH4 ReO4 ,
(NH4 )6 Mo7 O24 and (NH4 )4
W10 O32 as pre-cursors. The
catalytic activity is increased
almost one order by
addition of the optimized
amount of the modifier. The
modifica-tion also drastically
changed the selectivity: 1,5PeD is produced as a main
product in 80% selectivity
and 1,2-PeD is not produced
at all even when Rh/SiO2 is
modified with 0.06 mol/molRh of

Al2 O3 ). Performances of
Rh-based catalysts for THFA
decreases the number of molecules. hydrogenolysis
are
HO
Therefore, too high reaction temperature summarized in Table 2 [23
may hinder the formation of PeDs.
26].
Rh/SiO2
catalyzes
One typical mechanism of C O hydrogenolysis of aqueous
hydrogenolysis is the multi-step one THFA [23,24]. The main
composed of dehydration catalyzed by acid product is 1,2-PeD (62%
at
5.7%
and hydrogenation catalyzed by metal [7]. selectivity)
The hydrogenolysis of glycerol into 1,2- conversion at 393 K. The
selectivity to 1,5-PeD is 18%,
propanediol over the combination of Ru/C
and that to degradation
and acidic Amberlyst is a typical example products is 14%. Commercial
[1619]. In the case of THFA, one system Ru/C, copper chromite, and
composed of three separated steps has Raney Ni showed less
been known: dehydration of THFA to activity and much higher
dihydropyran, hydration of dihydropyran to selectivity to degradation
-hydroxyvaleraldehyde, and hydrogenation products [23], while copper
catalysts including copper
of -hydroxyvaleraldehyde to 1,5-PeD (Eq.
chromite have been known to
(1)) [20].
be
active
in
the
hydrogenolysis of C O bond
in the side chains of furan
OH
compounds such as furfural,
O
O
furfuryl alcohol and 5+ H 2O
hydroxymethylfurfural to give
alkyl-substituted furans such
step
types of mechanism proposed
may
This indirect system
requires
mechanisms
dehydration
of catalysts and reaction
of the intermediates
andof theglycerol, the include the two-hydrogenation

OH
(1)

mechanism
as
mentioned
above, the three-

step
dehydrogenetaionadditive.
The
dehydrationhydrogenation degradation sidemech-anism over copperreactions are also
catalysts and the directsuppressed by the
mechanism where hydridemodification. The
species on noble metaloptimum amount
directly
attacks
theof the modifier is
adsorbed sub-strate [21].0.50, 0.13 and
However, the mechanism of0.13 mol/mol-Rh
each system is still underfor Re, Mo and W,
debate, and in some casesrespectively.
different mechanisms haveHigher or lower
been pro-posed to veryamount of the
than
similar systems by differentmodifier
these
values
research groups.
decreases
the
catalytic activity.
The
catalytic
activity of the optimized catalysts decreases in the following order: Rh
(Re/Rh = 0.5) > Rh MoO
(W/Rh = 0.13).
However, in the
conditions of very
dilute THFA (1%
aqueous solution),
Rh MoOx/SiO2 is
rather
higher
activity than Rh
ReOx/SiO2
.
Therefore,
in
terms of obtaining
high yield of 1,5PeD,
Rh
MoOx/SiO2 is not
inferior
to
Rh
ReOx/SiO2
.
Lower
reaction
temperature and
longer
reaction
time is favorable
to the

138

Y. Nakagawa, K. Tomishige / Catalysis Today 195 (2012) 136143

Table 2
Selected examples of hydrogenolysis of THFA.
Catalyst

H2
[MPa]

THFA/water/catalyst
[g]

Temp. [K]

Rh/SiO2
Rh ReOx /SiO2 (Re/Rh = 0.5)
Rh ReOx /SiO2 (Re/Rh = 0.13)
Rh MoOx /SiO2 (Mo/Rh = 0.13)
Rh MoOx /SiO2 (Mo/Rh = 0.6)
Rh WOx /SiO2 (W/Rh = 0.13)
ReOx /SiO2
Ru/C
Copper chromite
Raney Ni
Rh ReOx /SiO2 (Re/Rh = 0.5)
Rh MoOx /SiO2 (Mo/Rh = 0.13)
Rh ReOx /C (Re/Rh = 0.25)
Rh ReOx /C (Re/Rh = 0.5)

8
8
8
8
8
8
8
8
8
8
8
8
8
3.4

1/19/0.05
1/19/0.05
1/19/0.05
1/19/0.05
1/19/0.05
1/19/0.05
1/19/0.05
1/19/0.05
1/19/0.5
1/19/0.5
1/19/0.1
1/19/0.1
1/19/0.1
9/171/1

393
393
393
393
393
393
393
393
453
453
373
373
373
393

4
4
4
4
4
4
4
4
4
4
36
24
24
4

MoOx /C (Mo/Rh = 0.1)

3.4

7/133/2

393

Rh

Time [h]

Conv. [%]

Products (selectivity [%])

Ref.

5.7
57
26
50
40
30
<0.1
5
0.6
0.2
96
94
99
47

1,5-PeD (18), 1,2-PeD (62), 1-PeOH (6)

1,5-PeD (94), 1-PeOH (4)
1,5-PeD (84), 1-PeOH (11)
1,5-PeD (96), 1-PeOH (4)
1,5-PeD (93), 1-PeOH (5)
1,5-PeD (85), 1-PeOH (6)
1,5-PeD (<0.1), 1,2-PeD (31), 1-PeOH (5)
1,5-PeD (15), 1,2-PeD (26), 1-PeOH (8)
1,5-PeD (<0.1), 1,2-PeD (9), 1-PeOH (3)
1,5-PeD (13), 1,2-PeD (13), 1-PeOH (9)
1,5-PeD (90), 1-PeOH (8)
1,5-PeD (90), 1-PeOH (9)
1,5-PeD (95), 1-PeOH (4)
1,5-PeD (97), 1-PeOH (3)

[23,24]
[23,24]
[24]
[24]
[24]
[24]
[23]
[23]
[23]
[23]
[24]
[24]
[25]
[26]

52

1,5-PeD (91), 1-PeOH (3)

[26]

PeD, pentanediol; PeOH, pentanol.

ReOx/SiO2 (Re/Rh =
0.13, 0.5) and Rh
higher 1,5-PeD yield. Higher temperature leads
overhydrogenol-ysis of 1,5-PeD to 1-PeOH. TheMoOx/SiO2 (Mo/Rh =
0.13) corresponds to the
maximum yield of 1,5-PeD is 86% over Rh ReOx/SiO2partial reduc-tion of
at 373 K using 5% THFA aqueous solution. The ReOx and MoOx to the
comparable yield of 85% is obtained over Rh valence of around +3
around
+4,
MoOx/SiO2 at 373 K in shorter reaction time (about and
respectively, in addition
2/3 of the time required for Rh ReO x/SiO2 ). Withoutto the total reduction of
Rh, monometallic ReOx/SiO2 , MoOx/SiO2 , andRh2 O3 [31].
WOx/SiO2 show almost no activity, indicating the
synergy between Rh and the additive metal.
The stability of the catalysts was checked by the
reuse exper-iments. The used catalyst was recovered
by centrifugation and reused. Rh ReOx/SiO2 shows
slight decrease in activity during reuses (79 and 65%
conversion (12 h reaction at 393 K) in the first and fifth
runs, respectively) while selectivities are not changed.
Slight Re leaching was observed by ICP analysis. On
the other hand, Rh MoOx/SiO2 can be reused without
loss of activity (53.5% and 53.0% conversion in the
first and fifth runs, respectively). The XRD patterns
and EXAFS spectra of fresh Rh MO x/SiO2 (M = Re
and Mo) after reduction are almost identical to those
of used catalysts.
The combination of Rh and Re can be applied for
carbon-supported catalysts [25]. We prepared Rh
ReOx/C by impregnating aqueous NH4 ReO4 on
commercial Rh/C. The optimum amount of Re is
Re/Rh = 0.25. The Rh ReOx/C (Re/Rh = 0.25) shows
slightly less activity than Rh ReOx/SiO2 (Re/Rh = 0.5)
and very high selectiv-ity to 1,5-PeD (95% in initial
stage). The highest yield of 1,5-PeD is 94%. Chia et
al. prepared Rh ReOx/C catalyst by sequentially
impregnating XC-72 carbon with aqueous RhCl3 and
NH4 ReO4 [26]. The Rh ReOx/C (Re/Rh = 0.5)
catalyst shows very high selectivity to 1,5-PeD (97%
selectivity at 47% conversion) at 393 K, similar to our
catalysts. They also prepared Rh MoOx/C from XC-72,
RhCl3 and (NH4 )6 Mo7 O24 . The Rh MoOx/C (Mo/Rh
= 0.1) has slightly less activity and selectivity to 1,5PeD than Rh ReOx/C. Supports other than C and
SiO2 are less explored.
3.2. Characterization of supported Rh
MOx (M = Re, Mo) catalysts
We characterized Rh ReOx/SiO2 and Rh
MoOx/SiO2 with vari-ous techniques [23,24,2931].
The TPR profiles of calcined Rh/SiO2 , Rh ReOx/SiO2
and Rh MoOx/SiO2 show that the reduction is stopped
below the temperature for the catalytic reaction (373
K). The amount of H2 consumption of Rh/SiO2 agrees
with the sto-ichiometry of the reduction of Rh 2 O3 to
Rh metal. The amount of H2 consumption of Rh

The peak temperature is

below the temperature
range
where
the
reduction of ReOx/SiO2
and
MoOx/SiO2
proceeds (533553 K
and
708713
K,
respectively).
These
data suggest that all the
added Re or Mo is
affected by the presence
of Rh species and the
reduction of Re and Mo
species is promoted
probably via spilt-over
hydrogen species from
Rh to Re and Mo. In the
case of Rh ReOx/SiO2 ,
we also performed Re
L3 -edge XANES to
determine the average
Re valence [29]. The
first peak in the L3 -edge
XANES is called as a
white line, and the white
line area in the L3 -edge
XANES is known to be
an
informa-tive
indication
of
the
electronic state. The
larger white line intensity
is
due
to
greater
electron vacancy in dorbital, indicating the
high valence state. The
ionic valence of Re
species
on
Rh
ReOx/SiO2
can
be
determined
by
the
relation between the
ionic valence and the
white line intensity of the
reference
compounds
such as metallic Re and
various rhenium oxides.
The average valence of
reduced Rh ReOx/SiO2
(Re/Rh
=
0.5)
determined from the
relation is +2.2.
In the XRD patterns
of
Rh/SiO2
,
Rh
ReOx/SiO2
and
Rh
MoOx/SiO2 after the
reduction or catalytic
use, a peak around 2 =

41 assigned to Rh
metal
is
detected

[23,24,29]. The Rh metal particle size is around 3 nm

and is hardly influenced by the presence of ReO x and
MoOx. The peak due to Re and Mo species is not
detected, indicating that the Re and Mo species is
highly dispersed. TEM analysis also shows the
presence of particles with average size of about 3 nm
in all of these catalysts.
The number of surface Rh atoms can be
determined by the mea-surement of the amount of
adsorbed CO because CO is adsorbed more
preferably on the surface of Rh atoms than of oxide
species at room temperature
[23,24,29,31]. The
number of surface atoms determined by XRD and CO
adsorption is shown in Table 3. In the case of reduced
Rh/SiO2 , the amount of adsorbed CO well accords
with the number of surface Rh atoms determined by
XRD peak width and Scherrers equation. On the
other hand, the amount of adsorbed CO on Rh
ReOx/SiO2 and Rh MoOx/SiO2 is significantly lower
than that of Rh/SiO2 although the average Rh metal
parti-cle sizes are similar. This behavior indicates that
the CO adsorption is suppressed by the presence of
ReOx or MoOx. The suppressed

Table 3
Results of XRD and CO adsorption of Rh/SiO2 , Rh
after reduction [31].

ReOx /SiO2 and Rh

MoOx /SiO2

Catalyst

Rh particle size
from XRD [nm]

Rhsurf /Rh
from XRD

CO adsorption
CO/Rh

Rh/SiO2
Rh ReOx /SiO2 (Re/Rh = 0.13)
Rh ReOx /SiO2 (Re/Rh = 0.5)

2.8
2.7
3.2

0.39
0.41
0.34

0.39
0.28
0.17

Rh MoOx /SiO2 (Mo/Rh = 0.13) 2.6

0.42
Y. Nakagawa, K. Tomishige / Catalysis Today 195 (2012) 136143

0.29

to distinguish between Mo
amount of CO adsorption agrees with the and Rh as a backscattering
additive amount of Re or Mo when the atom because the atomic
additive amount is low (M/Rh 0.13). This num-ber of Rh and Mo is
suggests that one Re or Mo atom inhibits similar. Curve fitting of Mo Kthe adsorption of approximately one COedge EXAFS of
molecule. At the same time, this means that Rh MoOx/SiO2 shows the presence of Mo
all added Re and Mo atoms interact with Rhbonds. The distance of Mo Rh (or
metal surface. In the cases of Rh MOx/SiO2comparable to those of Mo
with M/Rh > 0.13 (M = Re, Mo), the Rh Rh bond in Rh metal
suppressed amount of CO adsorption is(0.268 nm). This represents
lower than the additive amount, sug-gestingthat the Mo atoms are directly
that a part of added Re and Mo does notinteracted with Rh or other
contribute to the suppression of COMo atoms, unlike
adsorption by the way such as the formation the Mo O Rh or Mo O Mo, although the Mo
of multilayer structure and the location onThe small CN of Mo Rh (or
isolated Mo species on Rh
the support.
In order to characterize the interaction ofmetal surface, for example,
Re or Mo species with Rh metal particles, three-fold hollow site of Rh (1
Re L3 -edge, Mo K-edge and Rh K-edge 1 1) surface.
K-edge
EXAFS
EXAFS analyses were carried out (Table 4) Rh
[23,24,31]. The data of reduced freshanalyses of Rh/SiO2 and Rh
catalyst and the one after use is essentiallyMOx/SiO2 (M = Re, Mo) give
results consistent with those
identical [29,30]. In the case of Re L 3 -edgediscussed above. Rh O bond
EXAFS, it is easy to distinguish between Rh is not detected in these
and Re as a backscattering atom. Thecatalysts after use. The CN
(9.8) of Rh Rh bond in
curve fitting of the spec-tra of Rh
Rh/SiO2 is very smaller than
ReOx/SiO2 indicates the presence of Re O, that of bulk Rh metal with fcc
(CN
=
12),
Re Rh and Re Re bonds. The fitting of the structure
the formation of
Fig. 3. A model structure of Rh
spectra using only two different bonds (Resupporting
small metal parti-cles. The
O + Re Rh and Re O + Re Re) cannot give CN of Rh Rh (or Mo) in Rh
MoOx /SiO2 (Mo/Rh = 0.13) (I) and
a good fit. The presence of the Re O bond MoOx/SiO2 catalysts is nearly
Rh ReOx /SiO2 (Re/Rh = 0.13) (II)
indicates that Re species is in the partially equal to that of Rh/SiO . In
[31].
2
oxidized state, which is supported by the
the case of Rh ReOx/SiO2 ,
Reprinted with permission from
TPR and Re L3 - edge XANES results. The Rh Re and Rh Rh bonds are
Elsevier.
present
and
the
interaction
presence of Re Rh bond demonstrates the
interaction between Re species and Rhbetween ReOx species and
not. Formation of ReOx
metal surface is verified
metal particles. The bond length of the ReRh
cluster in the case of Rh
from the side of Rh. The CN
Rh bond (0.2660.268 nm) is similar to that
of Rh Rh on Rh ReOx/SiO2
ReOx/SiO2
lowers
the
of
with various Re contents is
number
of
Rh
atoms
Rh Rh bond in Rh metal (0.268 nm) and it isalmost
shorterthe
thansame
that of
as that of
adjoining additive atom than
suggesting
the
2 , of
bond length
Re
Rh O Rh bond in Rh2 O3 (0.301 nm). The Rh/SiO
in
the
case
of
Rh
similar size of Rh metal
bond (0.2710.273 nm) in Rh ReOx/SiO2 isparticles.
MoOx/SiO2 , which may
Based on the above
comparable to that of the Re Re bond in Re
cause the larger optimum
metal (0.274 nm). These results indicate characterization, a model
amount of Re (Re/Rh = 0.5)
that no oxygen atoms are located betweenstructure of Rh MoOx/SiO2
than Mo (Mo/Rh = 0.13).
Re atoms or between Rh and Re atoms.(Mo/Rh = 0.13) and Rh
The coordination number (CN) of the Re Rh
3.3. Reaction
bond (3.33.8) can be explained by theReOx/SiO2 (Re/Rh = 0.13) is
mechanism of the
adsorption of Re atoms at three-fold hollowdepicted (Fig. 3) [31]. The
selective hydrogenolysis
site of (1 1 1) surface and/or at four-fold surface Rh atoms with
of THFA to 1,5-PeD
hollow site of (1 0 0) surface. The CN of Re adjoining Mo or Re atom are
Re bond (2.02.8) is due to the cluster-ingrepresented by gray circles
of adsorbed Re species on the surface of and those without adjoin Re
As shown in Section 2,
Rh metal particles. The almost constant CN are represented by open
the indirect process of the
of the Re Rh bond in the range of Re/Rh circles. The former type of Rh
conversion of THFA to 1,5PeD via dihydropyran and
0.5 suggests that the ReOx clusters have 2-site is considered to be a
-hydroxyvaleraldehyde
has
dimensional structure on the Rh metalcatalytically active site, and
been developed. In order to
the
latter
type
is
surface.
check the contribution of this
reaction route, we evaluated
In the EXAFS analysis, it is impossible
the reaction of dihydropyran

over Rh ReOx/SiO2 (Re/Rh = 0.5) under the

Rh ReOx/SiO2 based on the

data of the reactivity of varH2 (8 MPa)
ious
relating
substrates
(Table 5) and the reaction
[32].
The
Rh-ReOx/SiO2 (50 mg), kinetics
of
water (19 g), 393 K, 4 hhydrogenolysis
tetrahydrofuran
and
2methyltetrahydrofuran hardly
proceeds over Rh ReOx/SiO2
hydrogenolysis over Rh ReOx/SiO2 .
. Rh/SiO2 shows rather
We
proposed
the
reaction
Therefore, the reaction route over Rh
higher activity for these
mechanism
of
the
substrates
than
Rh
ReOx/SiO2 is different from the indirecthydrogenolysis of THFA over
route via dihydropyran.
ReOx/SiO2 . Therefore, the
presence of H2 [32]. The result shows that
O
the formation of 1,5-PeD dehydration
accom-panies
the
tetrahydropyran
formation (12% selectivity). However, the 12 mmol
formation of tetrahydropyran is actually
below the detection limit in the THFA

presence of
tant. In

CH2 OH group in

addition, the

position

the substrate is very imporCH2 OH group is also

of the

Y.
Nakag
awa,
K.
Tomis
hige /
Cataly
sis
Today
195
(2012)
136
143

140
Table 4
EXAFS
curvefitting
results of
Rh/SiO2 ,
Rh

ReOx
/SiO2 and
Rh
R
[
1
0

Catalys
t
Edge

MoOx

/SiO2
after the
catalytic
use [31]. Shell

n
m
]

CN

1
.
9.85

Rh/SiO
2

Rh K

Rh

Rh

0
.
9.07

ReOx
/SiO2

Rh

Rh K

Rh

Rh

(Re/Rh
= 0.13)

Re L3

Rh

0
.
0.65

Re

Re

0
.
0.64

Re

Rh

2
.
6
7

0
.
0
1

2
.
3.87
2
.
6
8

Re

Re

21
..
2.064
6

Rh

ReOx
/SiO2

Rh K

Rh

Rh

9.0
0
.0
0.
49

2
.
1
3

0
.
0
6

0
.
0
2
1.
7
2
1
.
6

2
6.
0
6
.
8
0
0
8


(Re/Rh
= 0.5)

Re L3

Rh

0
.
1.78

Re

Re

0
.
1.39

Re

Rh

Rh K

Re

2
.
2.80

Re

2
.
6
70
.
3.68
0
.
0
4

2
.
1
3

Rh

Rh

Rh (or

0
.
10.68

Mo)

MoOx
/SiO2

Mo

2
.
0
1

0
.
1.18

Mo

Rh (or

Mo)

step.
Generally, H2
molecule is dis-sociated
important.
Hydrogenolysis
of
tetrahydro-5-to two hydrogen atoms
methylfurfuryl
alco-hol
and
tetrahydropyran-2-on the metal surface (H2
methanol smoothly proceeds over Rh ReOx/SiO2 to 2H).
form
1,6-hexanediol.
2-Alkoxyethanol
without
tetrahydrofuran or tetrahydropyran ring can be also
converted to ethanol and the corresponding alcohol.
On the other hand, hydrogenolysis of 3hydroxymethyltetrahydrofuran
hardly
pro-ceeds.
These reactivities show that the C O bond neighboring

In this case, it is known

that the reaction order

CH2 OH group is selectively dissociated over Rh

ReOx/SiO2 .
The reaction order with respect to the THFA
concentration (2060 wt%) over Rh ReOx/SiO2 and
Rh/SiO2 is almost zero and 0.4, respectively. The
reaction order indicated that Rh ReOx/SiO2 more
strongly adsorbs THFA than Rh/SiO2 , suggesting that
ReOx species is responsible for the strong adsorption
of THFA on Rh ReOx/SiO2 . Since it has been known
that adsorbed methoxy species is formed by the
interaction between methanol and ReOx [33], THFA is
thought to be adsorbed as a Re-alkoxide. It has been
established that molybdenum oxides adsorb alcohol to
form Mo-alkoxide species which serves as an
intermediate of the oxidation of alcohol [34].
The reaction order with respect to H2 pressure (2
8 MPa) is +1. The first reaction order with respect to
H2 means that the activation of H2 is an important

heterolytic activation (H2

with respect to H2
pressure is 1/2 in the
LangmuirHinshelwood
mechanism when the
reaction of the hydrogen
atom with the substrate
is a rate-determining
step. Another possible
H2

activation
+

0
.
0
1

(Mo/Rh
= 0.13) Mo K

0
.
1
1
2
.
7
3

2
.
6
8

is

H + H ) [35]. The
nature of the active
hydro-gen species was
also investigated using
ketone hydrogenation,
which has been known
to proceed by hydride
transfer [36,37]. The Rh
ReOx/SiO2 shows high
catalytic activity in the
acetol
(=hydroxyacetone)
hydrogenation and gives
1,2-propanediol as a
main product (Eq. (3)).

0
.
0
3

0
.
0
9

1
.
3.01

2
.
6
8

2
.
6
5

0
.
0
1

0
.
0
2

OH
O
13.5 mmol

H2 (8 MPa)
Rh-ReOx/SiO2 (50 mg),
water (19 g), 353 K, 4 h

OH +
OH
31%
(92% select.)

(3)
Table 5
Hydrogenolysis of various substrates over
Rh ReOx /SiO2 (Re/Rh = 0.5) and Rh/SiO2
[32].

On the other hand,

Pd/C, which is known to
activate H2 to two
hydrogen atoms, has no
activity in the same
reaction conditions, and
Rh/SiO2 also showed

very low activity in the

hydrogenation of acetol.
From the results of
acetol hydrogenation, it
is
suggested
that
hydride-like species are
formed by the activation
of H2 over

Catalyst

Rh

ReOx /SiO2

Substrate (amount [mmol])

(14)

Rh/SiO2

Rh

ReOx /SiO2

(12)

Rh/SiO2

(9.8)

Rh ReOx /SiO2

Rh

ReOx /SiO2

(8.5)
(11)

Rh ReOx /SiO2

Rh

(9.6)

ReOx /SiO2
Conditions:

Conv. [mmol]

Products (carbon-based selectivity [%])

0.2

1-Butanol (>99)

1.3

1-Butanol (>99)

0.1

2-Pentanol (90)

0.7

2-Pentanol (90)

0.3

2-Methyl-1,4-butanediol (45), 3-methyltetrahydrofuran (31)

4.0

1,5-Hexanediol (92), 2-hexanol (3)

3.6

Ethanol (100)

4.0
Substrate (5 wt solution, total 20 mL), catalyst (0.05
% aqueous
g), H2 (8 MPa), 393 K, 4 h.

Ethanol + 2-propanol (100)

Y. Nakagawa, K. Tomishige / Catalysis Today 195 (2012) 136143

Rh ReOx/SiO2 catalyst. The

formation of hydride species
means the heterolytic H2
activation which co-produces a
proton. The pres-ence of
neighboring positively charged
Re atom may induce the
formation
of
hydride(-like)
species on the Rh atom. In the
case that the hydrogenolysis
reaction can proceed by the
attack of proton and/or hydride,
the product selectivity is strongly
influenced by the stability of
cation and anion reaction
intermediates.
One
typi-cal
reaction scheme is SN 1-type
one that consists of protonation
of oxygen atom, dissociation of
C O bond to form carbocation
inter-mediate,
and
hydride
transfer (proton hydride
mechanism). In the THFA
hydrogenolysis, this proton
hydride mechanism can explain
the product distribution. As
shown in Eq. (4), 1,5-PeD is
formed
via
more
stable
secondary carbocation.
OH
OH

+H

HO
+H

OH

OH
O

O
H

+
H
+

H
O
tetrahydropyran-5methylfurfuryl alcohol,
the carbocations formed
(less stable)
by the proton attack are
both secondary ones,
(4)
suggesting
the
However, in fact, this proton hydride mechanismformation of both 1,5cannot explain the product distribution in thehexanediol and 1,2hydrogenolysis of tetrahydro-5-methylfurfuryl alcohol hexanediol (Eq. (5)).
and
2-isopropoxyethanol.
In
the
case
of

OH
OH
-

+H

HO
+H
OH

OH

Fig. 4. Proposed
mechanism of THFA

hydrogenolysis over Rh
ReOx /SiO2 [32].
Reprinted with

OH
permission from Elsevier.
+H

HO

This
is completely opposite to the experimental result
ReOx/SiO2 catalyzes the selective hydrogenolysis of 2that Rh
isopropoxyethanol
to
(5)ethanol and 2-propanol.
However, in fact, the formation of 1,2-hexanediol is notThis discussion denies
detected. Furthermore, in the hydrogenolysis of 2- the proton hydride
isopropoxyethanol by the proton attack, the formation mechanism. In addition,
of ethylene glycol and propane could be more the effect of acid
preferable than that of ethanol and 2-propanol judging addition to the catalytic
system is very small,
from the secondary cation intermediate as shown in
also
indicating
the
Eq. (6).
hydrogenolysis
mechanism is not the
proton hydride one. It
also suggests that the
proton-transfer step is
located after the ratedetermining step.
In
contrast,
the
mechanism
via
the
anion
intermediate
formed
by
the
regioselective attack of
hydride from the side of
CH2 OH group and
subsequent protonation
of the anion can explain
the product distributions
(Eqs. (7) and (8)). The
attack of hydride produces
alkoxide
intermediates, and the
difference of the stability
of
alkoxide
intermediates is thought
to be small, and the
product distribution is
not determined by the
stability
of
the
intermediates.

(R=H or CH3)

R O

OH

OH

+H+
HO

OH
R

(7)

(less stable)
HO
+

(6)

OH

+H

OH

O
HO
+

+H

OH +
HO
+

spec
ies
(iii).
Rea
ction
s of
the
prod
uced
alko
xide
with
prot
on
and

142

Y. Nakagawa, K. Tomishige / Catalysis Today 195 (2012) 136143

another substrate release products (iv).

The step (iv) also produces the alkoxide
of substrate, followed by step (ii) of the
next cycle.
The mechanism of Rh MoOx/SiO2
-catalyzed hydrogenolysis can be
similar. The product distributions in the
hydrogenolysis of THFA and 2alkoxyethanol and the reaction orders
with respect to substrate (THFA) and H 2
pressure over Rh MoOx/SiO2 are essentially the same as those over Rh
ReOx/SiO2 [24,31].
Chia et al. proposed another
mechanism for hydrogenolysis of
polyols and cyclic ethers including THFA
catalyzed by Rh ReOx/C [26]. Based on
the explanation, the presence of surface
acid sites, which is confirmed by NH3
TPD, is important. The acidic hydroxyl
groups on Re associated with Rh
donates proton to the substrate, leading
to the formation of carbenium ion
transition states. The authors argued
that the reactivity trends observed
experimentally such as the higher
selectivity to 1,5-PeD than 1,2-PeD are
consistent with the DFT-calculated
stabilization of resulting carbenium ion
structures that can be formed on ringopening or dehydration.
3.4. Miscellaneous systems
Buntara et al. use the combination of
Rh ReOx/SiO2 with solid acid catalysts
to
convert
tetrahydrofuran-2,5dimethanol, which is the totalhydrogenation
product
of
5hydroxymethylfurfural, to 1,6-hexanediol
[38]. Rh ReOx/SiO2 itself can catalyze
the hydrogenolysis of tetrahydrofuran2,5-dimethanol to 1,2,6-hexanetriol. The
combination with solid acid catalyst and
long reaction time enables the one-pot
conversion to 1,6-hexanediol and the
highest 1,6-hexanediol yield is 86%
using Nafion SAC-13 (Eq. (9)). Other
solid acids such as zeolites show similar
activities but lead to slightly lower
selectivities

O
O

(10 ml),
403 K,Table 6

24 h Hydrogenolysis of THFA over

Rh and Pd catalysts in scCO2
[38].

OH
O

Catalyst

Conv. [%]

Products (selectivity [%])

Rh/MCM-41
Rh/Al2 O3
Rh/C
Rh/SiO2
Pd/MCM-41
Pd/Al2 O3
Pd/C

81
60
35
30
51
33
49

1,5-PeD (91), 1-PeOH (9)

1,5-PeD (22), 1,2-PeD (51), 1-PeOH (51)
1,5-PeD (30), 1,2-PeD (42), 1-PeOH (20)
1,5-PeD (78), 1,2-PeD (11), 1-PeOH (8)
1,5-PeD (13), 1,2-PeD (77), 1-PeOH (10)
1,5-PeD (9), 1,2-PeD (1), 1-PeOH (48)
1,5-PeD (99), 1,2-PeD (0.3), 1-PeOH (0.5)

Conditions: Catalyst (0.1 g),

THFA (0.4 g), CO2 (14 MPa), H2
(4 MPa), 353 K, 24 h.

Rh/C and Rh/SiO2 show

less
activity
and
selectivity to 1,5-PeD than
Rh/MCM-41.
4. Catalysts based on
other active metals than
Rh
Although
Rh-based
catalysts are the most
active
in
the
hydrogenolysis
of
aqueous THFA in simple
monometallic cata-lysts,
there are some reports
using
catalysts
with
another active metal to
obtain good results. Xu et
al.
reported
the
development

of

Pt/Co2

AlO4 catalysts and their

performance in the direct
con-version of furfural to
1,5-PeD [40]. The best
catalyst is prepared by
co-precipitation
method
and modified with small
amount of Li. The 1,5PeD yield reaches 34.9%
(Eq. (10)). The time
course of the reaction
shows that 1,5-PeD is
produced
by
the
hydrogenolysis of furfuryl
alcohol intermediate and
the reaction route via
THFA to 1,5-PeD is
negligible. The authors
3+

H2
(1.
5
M
Pa
)
PtLi/Co
AlO
(0.2 g),
0.4 g

proposed that Co site is

mainly responsible for the
adsorption of C C and
the opening of the furan
ring, and Pt works for the
following hydrogenation
(Eq. (11)).
OH
HO

OH

+ HO

34.9%
etha
nol

16.2%
O

OH

+
31.3%

O1 compounds
17.5%OH

to
1,6-hexanediol.dione as a main
(81%
Application of the Rhproduct
ReOx/SiO2
-catalyzedselectivity at full
conversion) and
hydrogenation directly on
1,6-hexanediol
5-hydroxymethylfurfural
with only 7%
gave the for-mations of
selectivity.
1-hydroxyhexane-2,5HO

OH

0.8 mmol

HO

While
active and very
palladium
isselective (>99%
usually
a
lessat
49%
active element in Cconversion)
to
O hydrogenolysis1,5-PeD
in
[22],
Pd/C
isscCO (Table 6)
2
reported to be

O
Rh-ReO
OH
Nafion
14% SAC-13 (15 mg),
water (2 g), 393 K, 20 h

Pt

H2

(9)

(11)

[39].
Because
the activity of
Pd/C is lower
than Rh/MCM-41
(conversions of
48.9%

Chatterjee vs.
et al. use80.5% in
supercritical the same
carbon
condition
dioxide
s), Pd/C
(scCO2 ) aswas not
reac-tion
chosen
media in the
for
THFA
hydrogenolysi further
s (Table 6)study by
[39]. The usethe
of
scCO2authors.
leads a high
Iridiu
concentration m
lies
of
reactantjust
gas such asunder
H2 , whichrhodium
in
the
allows kinetic
periodic
control
oftable. It
reactions ashas been
opposed
toknown
limiting
ofthat
reaction ratesiridium
by
thecomplex
transport
ofes,
as
the gaseouswell as
reactant
rhodium
across
thecountergasliquid
parts,
interface.
Incan
activate
addition,
to
scCO2 is aH2
give
wellestablished hydride
ecologically complex
es. We
benign
have
reaction
very
medium.
Without anyrecently
additive, thereported
that
Ir
Rh/MCM-41
ReOx/Si
catalyst
shows
highO2
selectivity tocatalyzes
1,5-PeD (max.the
91.2%
athydrogen
80.5%
olysis of
conversion). glycerol
The authorsinto 1,3hypothesize propaned
that
theiol with
presence
ofmuch
higher
Rh2 O3 andselectivit
0

than
Rh particlesy
on Rh/MCM-Rh
41
asReOx/Si
confirmed by
XRD can beO2
the
reason[41,42].
behind
theThe
proposed
selective
mechani
formation ofsm
1,5-PeD.
based on
Rh/Al2 O3 , the catalyst
character
ization,
product
distributi
ons
in
the
hydrogen
olysis of
related
substrate
s,
and
the
kinetic
analysis
is

essentiall
y
the
same as
the
mechanis
m
proposed
by us for
Rh
ReOx/SiO
as
2
discussed

Y. Nakagawa, K. Tomishige / Catalysis Today 195 (2012) 136143

in Section 3.3. The application of the

iridium-based
catalysts
to
the
hydrogenolysis
of
tetrahydrofuran
derivatives is now in progress.
5. Conclusions and outlook

[9]

M.E. Zakrzewska,
E.
Bogel-ukasik,
R.
Bogel-ukasik, Chemical
Reviews
111
(2011)
397417.

[10]Vilonen,R.

Karinen,
K.
M.
Niemel,
ChemSusChem
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10021016.

[11]Corma, M.J.S.

Climent,
A.
Iborra, Green
Chemistry 13 (2011) 520

540.
Tetrahydrofuran
derivatives,
J.-P. Lange, E. van der
especially THFA, are promising sources[12]
Heide, J. van Buijtensen, R.
Price,
ChemSusChem,
in
of organic chemicals that are currently
press.
produced from fos-sil fuels. Recent[13]
N.
Merat,
C.
Godawa,
A.
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developments in catalysts such as
Journal
of
Chemical
rhodium-based ones modified with
Technology
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another metals have enabled the
Biotechnol-ogy
48
(1990) 145159.
conver-sion of THFA to 1,5-PeD in high
yields (85%). The formation of metal
bond between Rh metal particles and
partially reduced modifiers is a key to
the high selectivity. Hydrogenolysis of
tetrahydrofuran-2,5-dimethanol, which
can be produced from hex-oses via 5hydroxymethylfurfural, to 1,6-hexanediol
is an also very promising reaction route
in the conversions of biomass. Similar
cat-alyst systems to those for THFA
hydrogenolysis can be applied to the
hydrogenolysis of tetrahydrofuran-2,5dimethanol in combina-tion with solid
acid co-catalyst. To commercialize these
processes, further developments in
terms of the catalyst life and cost may
be necessary. Design of the reaction
systems including the reaction media
may be also important since the
separation of the reactant and products,
both of which have rather high boiling
points, are rather difficult. However, this
research field is young and growing
very rapidly, and the difficulties will be
overcome in the near future.

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B:
Environmental 105 (2011)
117127.